JP7041402B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition and a cured film obtained from the photosensitive resin composition.
More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high water repellency and oil repellency on the surface of a cured film, a cured film thereof, and various materials using the cured film. This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light-shielding material compatible with an inkjet method, or a partition wall material.

In recent years, a full-color display board manufacturing technique using an inkjet has been actively studied in the manufacturing process of a display element such as a thin film transistor (TFT) type liquid crystal display element and an organic EL (electroluminescence) element. For example, regarding the production of a color filter in a liquid crystal display element, light is blocked in a section (hereinafter referred to as a bank) that defines pre-patterned pixels in contrast to the conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method. There have been proposed a color filter formed of a photosensitive resin layer and dropping ink droplets on a region surrounded by the bank, and a method for manufacturing the same (Patent Document 1). Further, also in the organic EL display element, a method (Patent Document 2) has been proposed in which a bank is prepared in advance and ink to be a light emitting layer is dropped in the same manner to produce an organic EL display element.
However, when ink droplets are dropped on an area surrounded by banks by the inkjet method, the substrate is provided with a pro-inking property (hydrophilicity) in order to prevent the ink droplets from overflowing to the adjacent pixel beyond the bank. The surface needs to be water repellent.

In order to achieve the above objectives, it is proposed that the substrate can be made hydrophilic and the bank can be made water repellent by continuous plasma (ozone) treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment. (Patent Document 3), but the process is complicated. In addition, a proposal has been made to blend a fluorine-based surfactant or a fluorine-based polymer with a photosensitive organic thin film (Patent Document 4), but consideration is given to not only photosensitive but also coating film properties such as compatibility and addition amount. Not only are there many points to be considered, but UV ozone treatment during the hydrophilic treatment of the substrate reduces the water repellency of the surface, which is not practical.

On the other hand, conventionally, as a liquid-repellent bank, there is Japanese Patent Application Laid-Open No. 2015-172742 (Patent Document 5) as a negative type. Further, as a positive type, there is Japanese Patent Application Laid-Open No. 2012-22860 (Patent Document 6).

Japanese Unexamined Patent Publication No. 2000-187111 Japanese Unexamined Patent Publication No. 11-54270 Japanese Unexamined Patent Publication No. 2000-353594 Japanese Unexamined Patent Publication No. 10-197715 Japanese Unexamined Patent Publication No. 2015-172742 Japanese Unexamined Patent Publication No. 2012-22860

The present invention has been made in view of the above circumstances, and the problem to be solved thereof is used for a liquid crystal display element, an organic EL display element, etc., and is a cured film without plasma treatment, UV ozone treatment, or the like. It is an object of the present invention to form an image of a cured film having high water repellency and high oil repellency on the surface, little residue, and high lipophilicity and high lipophilicity on a substrate. In particular, in the case of substrate fabrication using inkjet, the purpose is to form an image of a cured film that can prevent ink droplets from overflowing to adjacent pixels beyond the bank.

As a result of diligent studies to achieve the above object, the present inventors have made at least one group and a bird selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group. The present invention has been completed by finding that water repellency and liquid repellency can be efficiently imparted to the film surface by forming a cured film from a composition containing a polymer having an alkoxysilyl group.

That is, the present invention relates to the following.
1. 1. A thermosetting photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D).
(A) Component: Polymer having the following groups (A1) and (A2) (A1) Liquid-repellent group (A2) Trialkoxysilyl group,
(B) Ingredient: Alkaline-soluble resin,
(C) Solvent,
Ingredient (D): Photosensitizer.
2. 2. The photosensitive resin composition according to 1 above, wherein the component (A) is a polymer further having the following (A3).
(A3): At least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group.
3. 3. The photosensitive resin composition according to 1 or 2 above, which satisfies at least one of the following (Z1) to (Z4).
(Z1): Further contains a cross-linking agent which is a component (E);
(Z2): The alkali-soluble resin of the component (B) further has a self-crosslinking group, or has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Have more;
(Z3): The component (D) is a photoradical generator, and the component (F) further contains a compound having two or more ethylenic double bonds;
(Z4): The component (D) is a photoacid generator, and the component (G) further contains a compound having two or more functional groups that form a covalent bond with the acid generated from the component (D).
4. (D) The photosensitive resin composition according to any one of 1 to 3 above, wherein the component is a quinonediazide compound.
5. 3. The photosensitive resin composition according to 3 above, wherein the component (D) is a quinonediazide compound and satisfies either (Z1) or (Z2).
6. Any of the above 1 to 5 above, wherein the liquid repellent group of the component (A) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group. The photosensitive resin composition according to Kaichi.
7. The photosensitive resin composition according to any one of claims 1 to 6, wherein the polymer of the component (A) is an acrylic polymer.
8. The photosensitive resin composition according to 7 above, wherein the acrylic polymer of the component (A) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene.
9. (B) The photosensitive resin composition according to any one of 1 to 8 above, wherein the alkali-soluble resin as a component has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
10. (B) The photosensitive resin composition according to any one of 1 to 9 above, which contains 0.1 parts by mass to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component.
11. The photosensitivity according to any one of 3 to 10 above, wherein the component (E) is 1 part by mass to 50 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). Sex resin composition.
12. A cured film made of a thermosetting product of the photosensitive resin composition according to any one of 1 to 11 above.
13. The display element having the cured film according to the above 12.
14. A display element having the cured film according to 12 above as an image forming partition wall.

The type photosensitive resin composition of the present invention can efficiently impart water repellency and liquid repellency to the film surface, and can form a cured film that does not impair the wettability of the pattern opening during development. ..

The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following components (A), (B), (C) solvent and (D).
(A) Component: Polymer having the following groups (A1) and (A2) (A1) Liquid-repellent group (A2) Trialkoxysilyl group,
(B) Ingredient: Alkaline-soluble resin,
(C) Solvent,
Ingredient (D): Photosensitizer.

The photosensitive resin composition of the present invention is preferably a polymer in which the component (A) further has the following (A3).
(A3): At least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group.

The photosensitive resin composition of the present invention preferably further satisfies at least one of the following (Z1) to (Z4).
(Z1): Further contains a cross-linking agent which is a component (E);
(Z2): The alkali-soluble resin of the component (B) further has a self-crosslinking group, or has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Have more;
(Z3): The component (D) is a photoradical generator, and the component (F) further contains a compound having two or more ethylenically polymerizable groups;
(Z4): The component (D) is a photoacid generator, and the component (G) further contains a compound having two or more functional groups that form a covalent bond with the acid generated from the component (D).

The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition in which the component (D) is a quinonediazide compound.

The details of each component will be described below.
<Ingredient (A)>
The component (A) is a polymer having the following groups (A1) and (A2), and more preferably a polymer having (A3).
(A1) Liquid-repellent group (A2) Trialkoxysilyl group (A3) At least one group selected from the group consisting of hydroxy group, carboxyl group, amide group and amino group.

In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester and acrylic polymer, and preferred polymers include acrylic polymers. Can be mentioned.

Here, the acrylic polymer is obtained by using a polymerizable unsaturated group such as an acrylic acid ester, a methacrylate ester, styrene, or maleimide, that is, a monomer having a polymerizable group containing a C = C double bond in the structure. Refers to the polymer to be used.

Examples of polyamic acid, polyimide, polyamide, and polyurea include polyamic acid obtained by reacting diamine with an acid dianhydride, polyimide obtained by immobilizing the polyamic acid, and polyamide or diamine obtained by reacting diamine with a dicarboxylic acid anhydride. Is a polyurea obtained by reacting with a diamine, and at least one group selected from the group consisting of at least one monomer having a fluoroalkyl group or a fluoroalkoxy group and a hydroxy group, a carboxyl group, an amide group and an amino group. Examples thereof include a polymer obtained from a monomer mixture containing at least one monomer having a polyurea and a monomer having a trialkoxysilyl group.

Examples of the polyurethane include polyurethane obtained by reacting a diol having a fluoroalkyl group or a fluoroalkoxy group with a diol having an amino group with a diisocyanate.

Examples of the phenol resin include a novolak resin obtained by polymerizing formaldehyde with a phenol having a fluoroalkyl group or a fluoroalkoxy group.

Examples of the epoxy resin include an epoxy resin obtained by reacting bisphenol A and / or bisphenol F having a fluoroalkyl group or a fluoroalkoxy group with glycidyl ether at the time of the bisphenol A and / or bisphenol F.

As the polysiloxane, a silane monomer mixture containing a trialkoxysilane having a fluoroalkyl group or a dialkoxysilanesilane having a fluoroalkyl group and a trialkoxysilane having an amino group or a dialkoxysilane having an amino group is polymerized. Examples thereof include the obtained polymer.

Examples of the polyester include a polyester obtained by reacting a dicarboxylic acid or a tetracarboxylic acid dianhydride with a diol having a fluoroalkyl group or a fluoroalkoxy group.

<(A1) Introduction of liquid-repellent group>
Examples of the liquid-repellent group include at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group.

The fluoroalkyl group has 3 to 10 carbon atoms, and preferably a fluoroalkyl group having 4 to 10 carbon atoms.
Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, and 3-perfluorobutyl group. -2-Hydroxypropyl group, 2- (perfluorohexyl) ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2- (perfluorooctyl) ethyl group, 3-perfluorooctyl-2-hydroxypropyl group , 2- (Perfluorodecyl) ethyl group, 2- (Perfluoro-3-methylbutyl) ethyl group, 3- (Perfluoro-3-methylbutyl) -2-hydroxypropyl group, 2- (Perfluoro-5-methyl) Hexyl) Ethyl group, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl group, 2- (perfluoro-7-methyloctyl) ethyl group, and 2- (perfluoro-7-methyloctyl)- 2-Hydroxypropyl group, etc. may be mentioned.

In order to introduce a fluoroalkyl group having 3 to 10 carbon atoms into the polymer which is the component (A) of the present invention, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms may be copolymerized.

Specific examples of the monomer having a fluoroalkyl group having 3 to 10 carbon atoms when the component (A) is an acrylic polymer include 2,2,2-trifluoroethyl acrylate and 2,2,2-tri. Fluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorobutyl) ) Ethyl methacrylate, 3-perfluorobutyl-2-hydroxypropyl acrylate, 3-perfluorobutyl-2-hydroxypropyl methacrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 3- Perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxypropyl methacrylate, 2- (perfluorooctyl) ethyl acrylate, 2- (perfluorooctyl) ethyl methacrylate, 3-perfluorooctyl-2- Hydroxypropyl Acrylate, 3-Perfluorooctyl-2-hydroxypropyl methacrylate, 2- (Perfluorodecyl) ethyl acrylate, 2- (Perfluorodecyl) ethyl methacrylate, 2- (Perfluoro-3-methylbutyl) ethyl acrylate, 2 -(Perfluoro-3-methylbutyl) ethyl methacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl methacrylate, 2- (per) Fluoro-5-methylhexyl ethyl acrylate, 2- (perfluoro-5-methylhexyl) ethyl methacrylate, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-) Methylhexyl) -2-hydroxypropyl methacrylate, 2- (perfluoro-7-methyloctyl) ethyl acrylate, 2- (perfluoro-7-methyloctyl) ethyl methacrylate, 2- (perfluoro-7-methyloctyl)- Examples thereof include 2-hydroxypropyl acrylate and 2- (perfluoro-7-methyloctyl) -2-hydroxypropyl methacrylate.

Examples of the polyfluoroether group include an Rf group (a) having a polyfluoroether structure represented by the following formula 1.
-(X-O) _n -Y ... Equation 1
In formula 1, X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorolated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and is in units of n. Representing the same or different groups, Y is a hydrogen atom (only when a fluorine atom is not bonded to a carbon atom adjacent to an oxygen atom adjacent to Y) and a monovalent saturated hydrocarbon having 1 to 20 carbon atoms. It represents a hydrogen group or a fluorolated monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, where n represents an integer of 2 to 50. However, the total number of fluorine atoms in Equation 1 is 2 or more.

As an embodiment of X and Y in the formula 1, preferably X is an alkylene group obtained by removing one hydrogen atom having 1 to 10 carbon atoms or a perfluorolated alkylene having 1 to 10 carbon atoms. It is a group and indicates the same group or a different group for each unit enclosed by n, and Y is an alkyl group or a carbon atom number 1 obtained by removing one hydrogen atom having 1 to 20 carbon atoms. Examples thereof include those showing 20 to 20 perfluorolated alkyl groups.

More preferably, as an embodiment of X and Y in the formula 1, X is a perfluorolated alkylene group having 1 to 10 carbon atoms, and the same group or a different group may be used for each unit enclosed in n. Indicated by Y, those indicating a perfluorolated alkyl group having 1 to 20 carbon atoms can be mentioned.

In Equation 1, n represents an integer of 2 to 50. n is preferably 2 to 30, more preferably 2 to 15. When n is 2 or more, the liquid repellency is good. When n is 50 or less, the polymer as the component (A) is a monomer having an Rf group (a), a monomer having a hydroxy group, a carboxyl group, an amide group, an amino group, or a trialkoxysilyl group, or the like. When synthesized by copolymerization with the monomer of, the compatibility of the monomer becomes good.

Further, the total number of carbon atoms in the Rf group (a) having the polyfluoroether structure represented by the formula 1 is preferably 2 to 50, more preferably 2 to 30. In this range, the polymer which is the component (A) exhibits good liquid repellency. Further, the polymer as the component (A) is copolymerized with a monomer having an Rf group (a) and a monomer having a hydroxy group, a carboxyl group, an amide group, an amino group, a trialkoxysilyl group or another monomer. When synthesized by, the compatibility of the monomers becomes good.

Specific examples of X include -CF _2- , -CF ₂ CF _2- , -CF ₂ CF ₂ CF _2- , -CF ₂ CF (CF ₃ )-, -CF ₂ CF ₂ CF ₂ CF ₂ -,- CF ₂ CF ₂ CF (CF ₃ )-and CF ₂ CF (CF ₃ ) CF _2- .

Specific examples of Y include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ ,-(CF ₂ ) ₂ CF ₃ ,-(CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF ₂ ) ₉ CF ₃ and (CF ₂ ) ₁₁ CF ₃ ,-(CF ₂ ) ₁₅ CF ₃ can be mentioned.

A preferred embodiment of the Rf group (a) having a polyfluoroether structure represented by the formula 1 is the Rf group (a) represented by the formula 2.

-C _p-1 F _{2 (p-1)} -O- (C _p F _2p -O) _n-1 -C _q F _{2q + 1} ... Equation 2
In Equation 2, p indicates an integer of 2 or 3, and each unit enclosed by n is the same group, q indicates an integer of 1 to 20, and n indicates an integer of 2 to 50.

Specifically, as the Rf group (a) represented by the formula 2,
-CF ₂ O (CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2 to 9),
-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₆ F ₁₃ (n is 2 to 6),
-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₃ F ₇ (n is 2 to 6)
Is preferably mentioned from the viewpoint of ease of synthesis.

The Rf groups (a) in the polymer which is the component (A) may be all the same or different.

The silyl ether group means a group in which the hydroxy group of the alcohol is protected by a trialkylsilyl group, and is preferably a group represented by the following formula.
-X ⁴ -Si (O-Si X ¹ X ² X ³ ) ₃
(In the formula, X ¹ , X ² , and X ³ independently represent an alkyl group having 1 to 3 carbon atoms, and X ⁴ represents an alkylene group having 1 to 6 carbon atoms.)

In order to introduce a silyl ether group into the polymer which is the component (A) of the present invention, a monomer having a silyl ether group may be copolymerized.

Examples of the monomer having a silyl ether group when the component (A) is an acrylic polymer include methacrylicoxypropyltris (trimethylsiloxy) silane and acrylicoxypropyltris (trimethylsiloxy) silane.

Examples of the polysiloxane group include a group (a) having a polysiloxane structure represented by the formula 3. Hereinafter, the group (a) having a polysiloxane structure represented by the formula 3 is referred to as a pSi group (a).
-(SiR ¹ R ² -O) _n -SiR ¹ R ² R ³ ... Equation 3
(However, R ¹ and R ² independently represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, R ³ represents hydrogen or an organic group having 1 to 10 carbon atoms, and n represents an integer of 1 to 200. show.).

R ¹ and R ² independently represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group, and may be the same or different for each syroxy unit. Since the polymer as the component (A) exhibits good liquid repellency, R ¹ and R ² are preferably hydrogen, methyl or phenyl groups, and further, all syroxy units R ¹ and R ² are used. Is preferably a methyl group. Further, R ³ may contain a nitrogen atom, an oxygen atom, or the like.

Examples of the method for introducing the pSi group (a) into the polymer (A) are a method of copolymerizing a monomer having a pSi group (a) and a compound having a pSi group (a) in a polymer having a reaction site. Examples thereof include various modification methods for reacting with the above, a method using a polymerization initiator having a pSi group (a), and the like.

Examples of the monomer having a pSi group (a) include CH ₂ = CHCOO (pSi) and CH ₂ = C (CH ₃ ) COO (pSi). However, pSi represents the pSi group (a). The monomer having a pSi group (a) may be used alone or in combination of two or more.

Examples of various modification methods for reacting a polymer having a reaction site with a compound having a pSi group (a) include the following methods.

A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having a carboxyl group at one end and a pSi group (a) at one end is reacted. A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group (a) at one end is reacted. A method in which a monomer having an epoxy group is copolymerized in advance, and then a compound having a mercapto group at one end and a pSi group (a) at one end is reacted. A method in which a monomer having an amino group is copolymerized in advance, and then a compound having a carboxyl group at one end and a pSi group (a) at one end is reacted.

A method in which a monomer having an amino group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group (a) at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an epoxy group at one end and a pSi group (a) at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having an amino group at one end and a pSi group (a) at one end is reacted. A method in which a monomer having a carboxyl group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a pSi group (a) at one end is reacted. A method in which a monomer having a hydroxyl group is copolymerized in advance, and then a compound having a silyl chloride group at one end and a PSi group (a) at one end is reacted.

The polymerization initiator having the pSi group (a) may contain a group having a divalent polysiloxane structure in the main chain of the initiator molecule, or may be monovalent in the terminal portion or the side chain of the initiator molecule. A group having a polysiloxane structure of the above may be contained. Initiator Examples of the initiator in which a group having a divalent polysiloxane structure is contained in the main chain of the molecule include a compound having a group having a divalent polysiloxane structure and an azo group alternately. Examples of commercially available products include VPS-1001 and VPS-0501 (all manufactured by Wako Pure Chemical Industries, Ltd.).

<Introduction of (A2) trialkoxysilyl group>
In order to introduce (A2) a trialkoxysilyl group into the polymer which is the component (A) of the present invention, a monomer having (A2) a trialkoxysilyl group may be copolymerized.

Examples of the monomer having a trialkoxysilyl group when the component (A) is an acrylic polymer include 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropylacrylate, 3-trimethoxysilylpropylmethacrylate, 3-. Examples thereof include triethoxysilylpropyl methacrylate.

When the component (A) is an acrylic polymer, the method for producing the polymer of the component (A) is a monomer having a liquid-repellent group, for example, a monomer having a fluoroalkyl group having 3 to 10 carbon atoms. A monomer having a polyfluoroether group, a monomer having a silyl ether group, at least one of a monomers having a polysiloxane group, and a monomer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. , A monomer having a trialkoxysilyl group, and optionally a monomer other than the above (hereinafter, also referred to as other monomer A) are polymerized in a solvent in the presence of a polymerization initiator at a temperature of 50 ° C to 110 ° C. Obtained by At that time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble polymer and the polymer having a specific functional group. Specific examples include the solvent described in (C) Solvent described later.

Specific examples of the other monomer A include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, and methoxytriethylene. Glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate , 8-Ethyl-8-tricyclodecylmethacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, Methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tri Examples thereof include cyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinylnaphthalene, vinylanthracene, vinyl biphenyl and the like. ..

The polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained as described above is poured under stirring such as diethyl ether or water to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Then, it can be made into a powder of a specific copolymer by normal temperature or heating and drying. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the solvent (C) described later and used as a solution.

<Introduction of at least one group selected from the group consisting of (A3) hydroxy group, carboxyl group, amide group and amino group>

In order to introduce at least one group selected from the group consisting of (A3) hydroxy group, carboxyl group, amide group and amino group into the polymer which is the component (A) of the present invention, (A3) hydroxy group and carboxyl group , A monomer having at least one group selected from the group consisting of an amide group and an amino group may be copolymerized.

Examples of the monomer having a carboxyl group when the component (A) is an acrylic polymer include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, and mono- (2- (2- (2). Examples thereof include methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

Examples of the monomer having a hydroxy group when the component (A) is an acrylic polymer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and 4-hydroxybutyl. Acrylic, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- ( Methacryloyloxy) ethyl ester, poly (ethylene glycol) acrylate, poly (propylene glycol) acrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2- Carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornen-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxy Examples thereof include phenylacrylamide, N-hydroxyphenylmethacrylate, p-hydroxyphenylacrylate, p-hydroxyphenylmethacrylate and the like. Of these, a monomer selected from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate is preferable.

Examples of the monomer having an amide group when the component (A) is an acrylic polymer include acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like. These can be used alone or in combination of two or more. Of these, methacrylamide is preferable.

Examples of the monomer having an amino group when the component (A) is an acrylic polymer include aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, aminopropyl methacrylate and the like, and these may be used alone or in combination of two or more. Can be used in combination.

In the polymer of the component (A), the amount of the liquid-repellent group (A1) introduced is preferably 5 mol% to 60 mol%, preferably 5 mol% to 40 mol%, based on all the repeating units. Is more preferable. If it is less than 5 mol%, it may not have a liquid-repellent effect. If it is more than 60 mol%, problems such as aggregation may occur.

In the polymer of the component (A), the amount of the (A2) trialkoxysilyl group introduced is preferably 5 mol% to 70 mol%, preferably 5 mol% to 50 mol%, based on all the repeating units. Is more preferable. If it is less than 5 mol%, problems may occur in the heat resistance and solvent resistance of the obtained film. If it is more than 70 mol%, it may affect the developability.

In the polymer of the component (A), the amount of at least one group selected from the group consisting of (A3) hydroxy group, carboxyl group, amide group and amino group is 5 to 60 mol% with respect to all the repeating units. It is preferably 5 to 40 mol%, and more preferably 5 to 40 mol%. If it is less than 5 mol%, problems may occur in the heat resistance and solvent resistance of the obtained film. If it is more than 60 mol%, the liquid-repellent repeating unit will be too small.

The number average molecular weight of the polymer of the component (A) is preferably 2,000 to 100,000. It is more preferably 3,000 to 50,000, still more preferably 4,000 to 10,000. If the number average molecular weight is greater than 100,000, residues may occur.

Further, in the present invention, the polymer of the component (A) may be a mixture of a plurality of specific copolymers.

<Ingredient (B)>
The component (B) of the present invention is a resin having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid, a boric acid and an active methylene group and an active methine group.

The active methylene group is a methylene group (-CH _2- ) having a carbonyl group at an adjacent position and having reactivity with a nucleophile. Further, in the present invention, the active methine group refers to a group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group in the active methylene group and having reactivity with a nucleating reagent.

（式（ｂ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。）As the active methylene group and the active methine group, a group represented by the following formula (b1) is more preferable.

(In formula (b1), R represents an alkyl group, an alkoxy group or a phenyl group, and the broken line represents a bond.)

In the above formula (b1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferable.
Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and the like.
Among them, a methyl group, an ethyl group, an n-propyl group and the like are preferable.

In the above formula (b1), examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and the like.
Among them, a methoxy group, an ethoxy group, an n-propoxy group and the like are preferable.

Examples of the group represented by the above formula (b1) include the following structures and the like. In the structural formula, the broken line represents a bond.

Among the above alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000. It is preferable to have.

The alkali-soluble resin of the component (B) may be any alkali-soluble resin having such a structure, and the type of the main chain skeleton and side chains of the polymer constituting the resin is not particularly limited.

However, the alkali-soluble resin of the component (B) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight is more than 50,000 and is excessive, development residue is likely to be generated and the sensitivity is greatly lowered, while if the number average molecular weight is less than 2,000 and is too small, the development is carried out. At that time, a considerable amount of film reduction may occur in the exposed area, resulting in insufficient curing.

Examples of the alkali-soluble resin as the component (B) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.

Further, in the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (B). In this case, the alkali-soluble resin of the component (B) may be a blend of a plurality of specific copolymers.

That is, the above-mentioned specific copolymer consists of a monomer that expresses alkali solubility, that is, a monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and a group of monomers copolymerizable with these monomers. It is a copolymer formed by using at least one selected monomer as an essential constituent unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is greater than 50,000, residues may occur.

The above-mentioned "monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group" includes a monomer having a phenolic hydroxy group and a monomer having a carboxyl group. These monomers are not limited to those having one phenolic hydroxy group or a carboxyl group, and may have a plurality of them.

Hereinafter, specific examples of the above-mentioned monomers will be given, but the present invention is not limited thereto.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.

Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.

The ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxy group and the polymerizable unsaturated group in the production of the alkali-soluble resin of the component (B) is all used in the production of the alkali-soluble resin of the component (B). Of the monomers, it is preferably 5 to 90 mol%, more preferably 10 to 60 mol%, and most preferably 10 to 30 mol%. When the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.

The alkali-soluble resin as the component (B) of the present invention is obtained by further copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further stabilizing the pattern shape after curing. Is preferable.

Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 2-hydroxyethyl methacrylate. Examples thereof include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and the like.

The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin of the component (B) is preferably 10 to 60% by mass, more preferably 5 to 50% by mass, and most preferably 20. It is 40% by mass. If the amount of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If it is 60% by mass or more, the alkali-soluble group of the component (B) may be insufficient, and the properties such as developability may be deteriorated.

The alkali-soluble resin which is the component (B) of the present invention is preferably obtained by further copolymerizing an N-substituted maleimide compound from the viewpoint of increasing the Tg of the copolymer.

N-substituted maleimide compound Examples of the maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, those having no aromatic ring are preferable, those having an alicyclic skeleton from the viewpoints of developability, transparency and heat resistance are more preferable, and cyclohexylmaleimide is most preferable.

The ratio of the N-substituted maleimide in the production of the alkali-soluble resin of the component (B) is preferably 10 to 60% by mass, more preferably 5 to 50% by mass, and most preferably 20 to 40% by mass. When the N-substituted maleimide is less than 10% by mass, the Tg of the copolymer is low, and the heat resistance may be inferior. If it is 60% by mass or more, the transparency may decrease.

When the photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin of the component (B) used in the present invention further has a self-crosslinking group, or has a hydroxy group, a carboxyl group, or an amide. It is preferably a copolymer further having a group (hereinafter, also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of a group and an amino group.

Examples of the self-crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate group.

Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group and the like.

When the self-crosslinking group or the crosslinkable group is contained in the alkali-soluble resin of the component (B), the content is 0.1 to 0.9 per unit of the repeating unit of the resin of the component (B). It is preferable, and from the viewpoint of developability and solvent resistance, 0.1 to 0.8 is more preferable.

The alkali-soluble resin of the component (B) further includes a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate group, and N-alkoxymethyl. Having a repeating unit having at least one selected from a crosslinkable group such as a group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, for example, having radical polymerizable and epoxy. An unsaturated compound having at least one selected from a crosslinkable group such as a group, an oxetane group, a vinyl group and a blocked isocyanate group and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group and an alkoxysilyl group. It may be copolymerized.

Examples of the unsaturated compound having a radical polymerizable property and an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. And so on.

Examples of the monomer having a radically polymerizable property and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.

Examples of the monomer having radical polymerizable property and further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.

Examples of unsaturated compounds having radical polymerizable properties and having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and α-n-butyl acrylate. Glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylate-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6, Examples thereof include 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Among these, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like. It is preferably used. These may be used alone or in combination.

Examples of the unsaturated compound having a radical polymerizable property and further having an oxetane group include (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3- Ethyl-oxetan, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetan, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) Methyl) -4-trifluoromethyloxetane is preferred, and 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane and the like are preferably used.

Examples of the monomer having a radically polymerizable property and further having a vinyl group include 2- (2-vinyloxyethoxy) ethyl acrylate and 2- (2-vinyloxyethoxy) ethyl methacrylate.

Examples of the monomer having radical polymerizable property and further having a blocked isocyanate group include 2- (0- (1'-methylpropanolamino) carboxyamino) ethyl methacrylate and 2- (3,5-dimethylpyrazolyl) methacrylate. Carbonylamino) ethyl and the like can be mentioned.

When the photosensitive resin composition of the present invention satisfies (Z1), it has radical polymerizable property, N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and block. Non having at least one group selected from a self-crosslinking group such as an isocyanate group and a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group. The constituent units derived from the saturated compound are preferably 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass, based on the total of all the repeating units of the alkali-soluble resin of the component (B). contains. If the structural unit is less than 10% by mass, the heat resistance and surface hardness of the obtained cured film tend to decrease, while if the amount of the structural unit exceeds 70% by mass, the radiation-sensitive resin composition is preserved. Stability tends to decrease.

Further, in the present invention, the acrylic polymer of the component (B) may be a copolymer formed by a monomer other than the above-mentioned monomer (hereinafter, referred to as other monomer) as a constituent unit. Specifically, the other monomer may be a monomer copolymerizable with at least one selected from the group consisting of the above-mentioned monomer having a carboxyl group and the monomer having a phenolic hydroxy group, and has the characteristics of the component (B). As long as it does not hurt, it is not particularly limited. Specific examples of such a monomer include acrylic acid ester compounds, methacrylic acid ester compounds, maleimides, acrylamide compounds, acrylonitrile, styrene compounds, vinyl compounds and the like.
Hereinafter, specific examples of the other monomers will be given, but the present invention is not limited thereto.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, and phenoxyethyl acrylate, 2,2,2-. Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone. Examples thereof include 2- (acryloyloxy) ethyl ester and poly (ethylene glycol) ethyl ether acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, and phenoxyethyl methacrylate, 2,2,2-. Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, Examples thereof include diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate and the like.

Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy. Examples thereof include methyl acrylamide and N-butoxymethylmethacrylamide.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allylglycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2. -Epoxy-5-hexene, 1,7-octadiene monoepoxiside and the like can be mentioned.

Examples of the styrene compound include styrene having no hydroxy group, for example, styrene, α-methylstyrene, chlorostyrene, bromostyrene and the like.

In the production of the alkali-soluble resin as the component (B), the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 20% by mass or less. If it is more than 80% by mass, the essential components are relatively reduced, so that it becomes difficult to sufficiently obtain the effect of the present invention.

The method for obtaining the alkali-soluble resin which is the component (B) used in the present invention is not particularly limited, but for example, a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or a phenolic hydroxy group are generated by the action of heat or acid. A monomer having at least one selected from the group consisting of groups, a monomer having a hydroxyalkyl group, optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate. A monomer having at least one group selected from a self-crosslinking group such as a group and a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group. It is obtained by carrying out a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent in which other copolymerizable monomers and a polymerization initiator and the like coexist, if desired. At that time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples include the solvent described in (C) Solvent described later.

The acrylic polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.

Further, the solution of the specific copolymer obtained as described above is poured under stirring such as diethyl ether or water to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Then, it can be made into a powder of a specific copolymer by normal temperature or heating and drying. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the solvent (C) described later and used as a solution.

Further, as the alkali-soluble resin of the component (B), a polyimide precursor such as a polyamic acid, a polyamic acid ester, a partially imidized polyamic acid, or a polyimide such as a carboxylic acid group-containing polyimide can be used, and they are alkaline. As long as it is soluble, the type can be used without particular limitation.

The polyamic acid which is a polyimide precursor can be generally obtained by polycondensing (a) a tetracarboxylic acid dianhydride compound and (b) a diamine compound.

The above (a) tetracarboxylic acid dianhydride compound is not particularly limited, and specific examples thereof include pyromellitic acid dianhydride, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 3,3'. , 4,4'-Benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride Aromatic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2, 3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetra Alicyclic tetracarboxylic acid dianhydride, such as carboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 1,2,3 Examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 4-butane tetracarboxylic acid dianhydride.
These may be used alone or in combination of two or more compounds.

Further, the diamine compound (b) is not particularly limited, and is, for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1. , 3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, Bis (4-amino-3-carboxyphenyl) sulfone, Bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'- Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino) -3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4- (4- (4-) Amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2 , 5-Diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-) Amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) Methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3) -Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoro Propane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbipheni , 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino) -4-Hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino) -4-Hydroxyphenoxy) phenyl] sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoro Diamine compounds having a phenolic hydroxy group such as propane, 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-) 3-Mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane and other diamine compounds having a thiophenol group, 1,3-diaminobenzene-4-sulfonic acid, 1,3- Diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, Examples thereof include diamine compounds having a sulfonic acid group such as 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis (2,6-ethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4, 4'-methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o- Trizine, m-tridine, 3,3', 5,5'-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aniline) hexafluoropropane, 2,2-bis (3-aniline) hexafluoropropane, 2,2-bis (3-amino-4) -Truyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2 -Diamines such as bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (trifluoromethyl) benzidine, etc. Compounds can be mentioned.
These may be used alone or in combination of two or more compounds.

When the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the compounding ratio of both compounds, that is, (b) the total number of moles of the diamine compound / (a). The total number of moles of the tetracarboxylic acid dianhydride compound is preferably 0.7 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the polyamic acid produced and the higher the molecular weight.

Further, when the diamine compound is excessively used for polymerization, the carboxylic acid anhydride can be reacted with the terminal amino group of the remaining polyamic acid to protect the terminal amino group.
Examples of such carboxylic acid anhydrides are phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydride phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid. Anhydrous, itaconic anhydride, tetrahydrophthalic anhydride and the like can be mentioned.

In the production of the polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from −20 ° C. to 150 ° C., preferably −5 ° C. to 100 ° C. In order to obtain a high molecular weight polyamic acid, a reaction temperature of 5 ° C. to 40 ° C. and a reaction time of 1 hour to 48 hours are appropriately selected. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select from a reaction temperature of 40 ° C. to 90 ° C. and a reaction time of 10 hours or more.
Further, when the terminal amino group is protected with acid anhydride, the reaction temperature can be selected from −20 ° C. to 150 ° C., preferably −5 ° C. to 100 ° C.

The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Examples of the solvent that can be used in this case include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, and dimethylsulfone. Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, Examples thereof include methyl isobutyl ketone and 2-heptanone. These may be used alone or in combination. Further, even if the solvent does not dissolve the polyamic acid, it may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate.

The solution containing the polyamic acid thus obtained can be used as it is for the preparation of the photosensitive resin composition. Further, the polyamic acid can be recovered and used by precipitating and isolating it in a poor solvent such as water, methanol or ethanol.

Further, any polyimide can be used as the component (B). The polyimide used in the present invention is obtained by chemically or thermally imidizing a polyimide precursor such as polyamic acid by 50% or more.

The polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
As a method for introducing a carboxyl group or a phenolic hydroxy group into a polyimide, a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of encapsulating an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method of reducing the imidization ratio to 99% or less when imidizing a polyimide precursor such as polyamic acid is used.

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
As a method of chemical imidization, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is generally used. Further, as a method of thermal imidization, a method of heating a polyimide precursor solution while dehydrating it at a temperature of 180 ° C. to 250 ° C. is generally used.

Further, as the alkali-soluble resin of the component (B), a phenol novolac resin can be further used.

Further, as the alkali-soluble resin of the component (B), a polyester polycarboxylic acid can also be used. Polyester polycarboxylic acids can be obtained from acid dianhydrides and diols by the method described in WO2009 / 051186.
Examples of the acid dianhydride include the above-mentioned (a) tetracarboxylic dianhydride.
Examples of the diol include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. , 1,4-Cyclohexanedimethanol, 1,3-Cyclohexanedimethanol, alicyclic diols such as 1,4-cyclohexanedimethanol, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol. And the like, aliphatic diols and the like can be mentioned.

Further, in the present invention, the alkali-soluble resin of the component (B) may be a mixture of a plurality of types of alkali-soluble resins.

The ratio of the component (A) to the component (B) is 0.1 part by mass to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B).

<(C) Solvent>
The solvent (C) used in the present invention dissolves the component (A), the component (B), and, if necessary, the component (D), the component (E), the component (F), and the component (G) described later. Moreover, the solvent is not particularly limited as long as it dissolves the component (H) described later and other additives added as desired, and the solvent has such a dissolving ability.

Examples of such (C) solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , 2-Hydroxypropionate, 2-hydroxy-2-methylpropionate, ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-ethoxypropionate ethyl, 3-ethoxypropionate methyl, pyruvate methyl, pyruvate ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and Examples thereof include N-methylpyrrolidone.

These solvents can be used alone or in combination of two or more.
Among these (C) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate and the like have good coating properties and are safe. Is preferable from the viewpoint of high. These solvents are generally used as solvents for photoresist materials.

<(D) component>
Examples of the photosensitive agent as the component (D) include (D-1) 1,2-quinonediazide compound, (D-2) photoradical generator, and (D-3) photoacid generator.

(D-1) The 1,2-quinonediazide compound is a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, and these hydroxyl groups or amino groups (both hydroxyl groups and amino groups). Of the total amount thereof), preferably 10 mol% to 100 mol%, particularly preferably 20 mol% to 95 mol% was esterified or amidated with 1,2-quinonediazide sulfonic acid. Compounds can be used.
Examples of the 1,2-quinone diazido sulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2-. Examples thereof include diazido-4-sulfonic acid, and the chloride of 1,2-quinonediazide sulfonic acid can be used in the reaction with the above-mentioned compound having either or both of a hydroxy group and an amino group.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallicate, ethyl gallicate, 1,3,3-tris (4-hydroxyphenyl). Butane, 4,4-isopropridenediphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4- Hexafluoroisopropyridenediphenol, 4,4', 4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1- [4- [1- (4-hydroxy) Phenyl) -1-methylethyl] phenyl] etiliden] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,3,4 , 4'-Tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, phenolic compounds such as 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol , 4-Butanol, Cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate and other aliphatic alcohols. Can be mentioned.

Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. , 4,4'-Diaminophenylmethane, 4,4'-diaminodiphenyl ether, and other anilines, aminocyclohexane can be mentioned.

Further, examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diaminophenol. 4,4'-Diamino-4''-hydroxytriphenylmethane, 4-amino-4', 4''-dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, bis (4-Amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy) -5-Hydroxyphenyl) Aminophenols such as hexafluoropropane, alkanolamines such as 2-aminoethanol, 3-aminopropanol and 4-aminocyclohexanol can be mentioned.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content when the compound having a quinonediazide group of the component (D-1) is contained is the component (A) and the component (B). It is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, and further preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass in total. If it is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developing solution becomes small, and patterning by development may be difficult. On the other hand, if it exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is lowered, or the component (D-1) absorbs light and the cured film is formed. It may reduce transparency.

(D-2) The photoradical generator is not particularly limited as long as it generates radicals by exposure. Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrene, benzoin methyl ether, and benzoin ethyl. Benzoin ethers such as ether and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5- Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-Triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4) -Morphorinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole , 2-Trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and other halomethyloxadiazole compounds, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- S-Triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxy Styryl-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Methyl-S-triazine, halomethyl-S-triazine compounds such as 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-Diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, benzoyl methyl benzoate, 4-benzoyl -4'-Methyldiphenylsulfide, benzylmethylketal, dimethylaminobenzoate, p-dimethylaminobenzoate isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2 , 4-dimethylthioxanthone, isopropylthioxanthone, 1- (4-phenylthiophenyl) -1,2-octanedione-2- (O-benzoyloxime), etanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1 -[4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphinoxide, diphenyl (2,4,6-trimethylbenzoyl) phosphinoxide, 2-methyl-1- [4 -(Methylthio) phenyl] -2- (4-morpholinyl) -1-propanol and the like.
The above-mentioned photoradical generator is easily available as a commercial product, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, and IRGACURE 819. 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (above, BASF) , TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, Examples thereof include TAZ-118, TAZ-122, TAZ-123, TAZ-140, and TAZ-204 (all manufactured by Midori Kagaku Co., Ltd.).
These photoradical generators can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains the component (D-2), the content is preferably 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 0.5 parts by mass to 20 parts by mass, and particularly preferably 1 part by mass to 15 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. On the other hand, if this ratio is excessive, the transmittance of the coating film may decrease or development defects in the unexposed portion may occur.

The photoacid generator of (D-3) is not particularly limited as long as it is a compound that photodecomposes to generate an acid when irradiated with ultraviolet rays. Examples of the acid generated when the photoacid generator is photodecomposed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-. Toluene sulfonic acid, campha sulfonic acid, trifluoromethane sulfonic acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mesitylene sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid and other sulfonic acids Examples thereof include acid or its hydrate and salt.

Examples of the photoacid generator include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. , And a cyano group-containing oxime sulfonate compound and the like. Any of the conventionally known or conventionally used photoacid generators can be applied in the present invention without particular limitation. In the present invention, the photoacid generator of the component (D) may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

When the photosensitive resin composition of the present embodiment contains the component (D-3), the content thereof is preferably 0.01 mass based on 100 parts by mass of the total of the component (A) and the component (B). It is 20 parts by mass, more preferably 0.1 part by mass to 10 parts by mass, and further preferably 0.5 part by mass to 8 parts by mass. By setting the content of the component (D-3) to 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, the unexposed part may be poorly developed or the storage stability of the composition may be lowered.

<(E) component>
The component (E) is a cross-linking agent, which is introduced into the composition when the photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridging structure by a thermal reaction with a thermally reactive moiety (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (B). Specific examples are given below, but the present invention is not limited to these. The heat cross-linking agent is, for example, selected from (E1) a cross-linking compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, and (E2) a cross-linking compound represented by the following formula (2). Is preferable. These cross-linking agents can be used alone or in combination of two or more.

When the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and the hydroxymethyl group of the component (E1) is exposed to a high temperature during heat curing, the crosslinking reaction proceeds by the dehydration condensation reaction. .. Examples of such compounds include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

Specific examples of alkoxymethylated glycol uryl include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycol uryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercial products, compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Co., Ltd. (high condensation type, trade name: Beccamin () Registered trademarks) J-300S, P-955, N) and the like.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. As commercial products, methoxymethyl type melamine compound manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)) ) 506, 508), Sanwa Chemical's methoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MS-001, same MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nicarac (registered trademark) MX-45, MX-410, MX-302), etc. Can be mentioned.

Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (registered trademark). Mitsui Cytec Co., Ltd.) and the like.

Specific examples of the phenoplast-based compound include, for example, 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, 3 , 3', 5,5'-tetrax (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methyl) Ethiliden) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene) bis [2,6-- Bis (hydroxymethyl) phenol], 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 2,6-bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2, , 6-bis (methoxymethyl) -4-methoxyphenol, 3,3', 5,5'-tetrakis (methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-methoxy-5) -Methylbenzenemethanol), 4,4'-(1-methylethylidene) bis [2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-methyl-6-methoxymethylphenol], 4, Examples thereof include 4'-(1-methylethylidene) bis [2,6-bis (methoxymethyl) phenol], 4,4'-methylenebis [2,6-bis (methoxymethyl) phenol], and the like. It can also be obtained as a commercially available product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA ( As mentioned above, Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.

Further, as the component (E1), an acrylamide compound substituted with a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or an alkoxymethyl group or Polymers made using methacrylamide compounds can also be used.

Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

（式中、ｋは２乃至１０の整数、ｍは０乃至４の整数を示し、Ｒ¹¹はｋ価の有機基を表す）Further, the photosensitive resin composition of the present invention can contain a crosslinkable compound represented by the following formula (2) as the component (E2).

(In the formula, k is an integer of 2 to 10, m is an integer of 0 to 4, and R ¹¹ is an organic group having a k valence).

The component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (2). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.

Commercially available products include Epolide GT-401, GT-403, GT-301, GT-302, Selokiside 2021, Selokiside 3000 (trade name manufactured by Daicel Chemical Industry Co., Ltd.), and Denacol, which is an alicyclic epoxy resin. EX-252 (trade name made by Nagase ChemteX Corporation), CY175, CY177, CY179 (above, product name made by CIBA-GEIGY AG), Araldite CY-182, CY-192, CY-184 (above). , CIBA-GEIGY AG product name), Epicron 200, 400 (product name of DIC Co., Ltd.), Epicoat 871, 872 (product name of Yuka Shell Epoxy Co., Ltd.), ED -5661, ED-5662 (hereinafter, product name manufactured by Ceranies Coating Co., Ltd.), and the like can be mentioned. In addition, these crosslinkable compounds can be used alone or in combination of two or more.

Among these, the compounds represented by the formulas E2-1 and E2-2, which have a cyclohexene oxide structure from the viewpoint of process resistance such as heat resistance, solvent resistance, long-term firing resistance, and transparency, Eporide. GT-401, GT-403, GT-301, GT-302, sinterside 2021, and seroside 3000 are preferable.

Further, as the E component, a bridging structure is formed by a thermal reaction with a heat-reactive site (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (B) other than those shown as the component (E1) and the component (E2). Compounds that can be formed can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane. Didiol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N', -Tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and N, N, N', N',-tetraglycidyl-4, 4'-diaminodiphenylmethane, etc. Epoxy compound, VESTANAT B1358 / 100, VESTAGON BF 1540 (above, isocyanurate-type modified polyisocyanate, manufactured by Degusa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (above, isocyanurate-type modification). Examples thereof include polyisocyanates and isocyanate compounds such as those manufactured by Mitsui Kagaku Co., Ltd.

Further, as the E component, a polymer having two or more structures capable of forming a bridging structure by a thermal reaction with the thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (B) can be used. can. Specifically, 3-methacryloxypropyltrimethoxy, a polymer produced using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethylmethacrylate, and 3,4-epoxycyclohexylmethylmethacrylate. Polymers manufactured using compounds having an alkoxysilyl group such as silane, 2-isocyanatoethyl methacrylate (Kalens MOI [registered trademark], manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (Kalens AOI [ Registered trademark], compounds having an isocyanate group such as those manufactured by Showa Denko Co., Ltd., or 2- (0- [1'-methylpropanolamino] carboxyamino) ethyl methacrylate (Carens MOI-BM [registered trademark], Showa Denko Co., Ltd.), 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (Carens MOI-BP [registered trademark], Showa Denko Co., Ltd.) and other compounds having a blocked isocyanate group. Examples include polymers manufactured using. These compounds may be used alone or in combination of two or more to produce a polymer, or may be combined with other compounds to produce a polymer.

When the component (B) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and a group represented by an amino group, the hydroxy group, the carboxyl group, the amide group, and the like. A compound having two or more groups represented by an amino group can be used as the component (E).

These crosslinkable compounds can be used alone or in combination of two or more.

When the component (E) is selected as the cross-linking agent in the photosensitive resin composition of the present invention, the content thereof is 1 part by mass to 50 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). It is preferably 1 part by mass to 40 parts by mass, and more preferably 1 part by mass to 30 parts by mass. When the content of the crosslinkable compound is low, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation is improved. May not be obtained. On the other hand, when it exceeds 50 parts by mass, an uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation are lowered, and the photosensitive resin composition is formed. Storage stability may deteriorate.

<(F) component>
The component (F) is a compound having two or more ethylenically polymerizable groups. The term "compound having two or more ethylenically polymerizable groups" as used herein means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the molecular ends. , Those polymerizable groups mean at least one type of polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group.
The compound having two or more ethylenically polymerizable groups as the component (F) has good compatibility with each component in the solution of the negative type photosensitive resin composition in the photosensitive resin composition of the present invention. Moreover, from the viewpoint of not affecting the developability, a compound having a molecular weight (weight average molecular weight when the compound is a polymer) of 1,000 or less is preferable.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and penta. Elythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropanetetraacrylate, tetramethylolpropanetetramethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, 1,3,5-Triacrylloyl hexahydro-S-triazine, 1,3,5-trimethacryloyl hexahydro-S-triazine, tris (hydroxyethylacryloyl) isocyanurate, tris (hydroxyethylmethacryloyl) isocyanurate, triacryloyl Formal, Trimethacryloylformal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol di Acrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N, N'-bis (acryloyl) ) Cysteine, N, N'-bis (methacryloyl) cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate , Bisphenol S dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, diallylate Examples thereof include rubisphenol A, o-diallyl bisphenol A, diallyl maleate, and triallyl trimellitate.

The above polyfunctional acrylate compound can be easily obtained as a commercially available product, and specific examples thereof include, for example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, and D-330. DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, TPA-330. PET-30, RP-1040 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, Same M-8560, same M-9050 (above, manufactured by Toa Gosei Co., Ltd.), Viscort 295, same 300, same 360, same GPT, same 3PA, same 400, same 260, same 312, same as 335HP (above, Osaka) Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD -TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900 , BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and the like.
These compounds having two or more ethylenically polymerizable groups can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains the component (F), the content thereof is 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Is preferable, and more preferably 10 parts by mass to 150 parts by mass, and particularly preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. On the other hand, if this ratio is excessive, tack may occur on the coating film after prebaking, or the unexposed portion may be poorly dissolved during development.

<(G) component>
The component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups forming a covalent bond with an acid. Examples of the functional group that forms a covalent bond with such an acid include an epoxy group, an alkoxymethyl group, and a hydroxymethyl group.

Examples of the compound having two or more epoxy groups include tris (2,3-epoxide propyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxide ethyl) cyclohexane, and glycerol. Triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylate diglycidyl Ester, 4,4'-methylenebis (N, N-diglycidyl aniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethanetriglycidyl ether and bisphenol-A-diglycidyl ether, And pentaerythritol polyglycidyl ether and the like.

Further, as the compound having two or more epoxy groups, a commercially available compound may be used because it is easily available. Specific examples (trade names) are given below, but the present invention is not limited to these: epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Toto Kasei Co., Ltd.); Epolide GT-401, the same. Epoxy resin having a cyclohexene oxide structure such as GT-403, GT-301, GT-302, seroxide 2021, seroxide 3000 (manufactured by Daicel Chemical Industry Co., Ltd.); Epicoat 1001, 1002, 1003, 1004, Bisphenol A type epoxy resin such as 1007, 1009, 1010, 828 (all manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)); Epicoat 807 (Oilized Shell Epoxy Co., Ltd.) Bisphenol F type epoxy resin (currently manufactured by Japan Epoxy Resin Co., Ltd.); Epicoat 152, 154 (currently manufactured by Yuka Shell Epoxy Co., Ltd. (currently manufactured by Japan Epoxy Resin Co., Ltd.)), EPPN201, 202. Phenol novolak type epoxy resin (above, manufactured by Nippon Kayaku Co., Ltd.); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.) ), Epicoat 180S75 (oiled shell epoxy Co., Ltd. (currently manufactured by Japan Epoxy Resin Co., Ltd.)) and other cresol novolac type epoxy resins; Denacol EX-252 (manufactured by Nagase Chemtex Co., Ltd.), CY175, CY177 , CY179, Araldite CY-182, CY-192, CY-184 (above, manufactured by CIBA-GEIGY AG), Epoxy 200, 400 (above, Dainippon Ink and Chemicals Co., Ltd.) (currently DIC Co., Ltd.) )), Epicoat 871, 872 (above, oiled shell epoxy Co., Ltd. (currently manufactured by Japan Epoxy Resin Co., Ltd.)), ED-5661, ED-5662 (above, manufactured by Ceranies Coating Co., Ltd.) The same alicyclic epoxy resin; Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX. An aliphatic polyglycidyl ether such as 313, EX-314, and EX-321 (manufactured by Nagase ChemteX Corporation).

Further, as the compound having two or more epoxy groups, a polymer having an epoxy group can also be used.
The polymer having an epoxy group can be produced, for example, by addition polymerization using an addition-polymerizable monomer having an epoxy group. Examples thereof include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and compression polymerization polymers such as epoxy novolak. ..

Alternatively, the polymer having an epoxy group can also be produced by reacting a polymer compound having a hydroxy group with a compound having an epoxy group such as epichlorohydrin and glycidyltosilate.

The weight average molecular weight of such a polymer is, for example, 300 to 20,000.

Compounds having two or more of these epoxy groups can be used alone or in combination of two or more.

Examples of the compound having two or more substituents selected from the alkoxymethyl group and the hydroxymethyl group include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast-based compounds. ..

Specific examples of the alkoxymethylated glycol uryl are as described in the above paragraph [0151].

Specific examples of the alkoxymethylated benzoguanamine are as described in the above paragraph [0152].

Specific examples of the alkoxymethylated melamine are as described in the above paragraph [0153].

Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 (registered trademark). Mitsui Cytec Co., Ltd.) and the like.

Specific examples of the phenoplast-based compound are as described in the above paragraph [0155].

Further, as the component (G), an acrylamide compound substituted with a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or an alkoxymethyl group or Polymers made using methacrylamide compounds can also be used.

Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

When the photosensitive resin composition of the present invention contains a compound having two or more functional groups forming a covalent bond with the acid of the component (G), the content is 100 in total of the components (A) and (B). It is preferably 5 parts by mass to 200 parts by mass, more preferably 50 parts by mass to 150 parts by mass based on the parts by mass. If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease, while if it is excessive, the developability of the unexposed portion may decrease and the residual film or residue may be deteriorated. It may be the cause.

<Other additives>
Further, the photosensitive resin composition of the present invention may be a rheology adjuster, a pigment, a dye, a storage stabilizer, an antifoaming agent, an adhesion accelerator, or a polyvalent as necessary, as long as the effect of the present invention is not impaired. It can contain a dissolution accelerator such as phenol and polyvalent carboxylic acid.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following components (A), (B), (C) solvent and (D), and if desired, the component (E). , A compound having two or more ethylenically polymerizable groups of the component (F), a compound having two or more functional groups forming a covalent bond with the acid of the component (G), and one or more of other additives. Is a composition that can further contain.
(A) component: The following groups (A1) and (A2), if desired, a polymer having (A3) (A1) liquid-repellent group (A2) trialkoxysilyl group (A3) hydroxy group, carboxyl group, amide group and At least one group selected from the group consisting of amino groups,
(B) Ingredient: Alkaline-soluble resin,
(C) Solvent,
Ingredient (D): Photosensitizer.

Among them, preferable examples of the photosensitive resin composition of the present invention are as follows.
[1]: A photosensitive resin composition containing 0.1 part by mass to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B), and these components are dissolved in the solvent (C).
[2]: The component (A) is contained in an amount of 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (B), and the component (D) is contained in an amount of 5 parts by mass to 100 parts by mass. C) A photosensitive resin composition dissolved in a solvent, wherein the component (D) is a component (D-1).
[3]: The component (A) is contained in an amount of 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (B), and the component (D) is contained in an amount of 5 parts by mass to 100 parts by mass. C) A photosensitive resin composition dissolved in a solvent, and further, the cross-linking agent which is the component (E) is added in an amount of 1 part by mass or more based on 100 parts by mass of the total of the components (A) and (B). A photosensitive resin composition containing 50 parts by mass, wherein the component (D) is a component (D-1).
[4]: 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (B), and 5 to 200 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). Contains 0.1 to 30 parts by mass of (D) component with respect to 100 parts by mass of the total of (F) component, (A) component, (B) component and (F) component, and these are (C). A photosensitive resin composition dissolved in a solvent, wherein the component (D) is a component (D-2).

The proportion of the solid content in the photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass, and for example. It is 5% by mass to 60% by mass, or 10% by mass to 50% by mass. Here, the solid content means the one obtained by removing the solvent (C) from all the components of the photosensitive resin composition.

The method for preparing the photosensitive resin composition of the present invention is not particularly limited, but as the method for preparing the photosensitive resin composition, for example, the component (A) (specific polymer) is dissolved in the solvent (C), and (B) is dissolved in this solution. With an alkali-soluble resin as a component, a photosensitizer as a component (D), a cross-linking agent as a component (E), a compound having two or more ethylenically polymerizable groups as a component (F), and an acid as a component (G), if necessary. A method in which a compound having two or more functional groups forming a covalent bond is mixed at a predetermined ratio to obtain a uniform solution, or at an appropriate stage of this preparation method, other additives are further added as necessary. And a method of mixing.

In the preparation of the photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the solvent (C) can be used as it is, and in this case, the solution of the component (A) is described above. Similarly, when the component (B), the component (D), and if necessary, the component (E), the component (F), the component (G), etc. are added to form a uniform solution, the component (C) is further adjusted for the purpose of adjusting the concentration. ) An additional solvent may be added. At this time, the solvent (C) used in the process of forming the specific copolymer and the solvent (C) used for adjusting the concentration at the time of preparing the photosensitive resin composition may be the same or different. May be good.

Therefore, it is preferable that the prepared solution of the photosensitive resin composition is used after being filtered using a filter having a pore size of about 0.2 μm or the like.

<Coating film and cured film>
The photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.). A coating film is formed by applying by rotary coating, sink coating, roll coating, slit coating, rotary coating following the slit, inkjet coating, etc., and then pre-drying with a hot plate or oven. Can be done. Then, by heat-treating this coating film, a photosensitive resin film is formed.

As the conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from a temperature range of 70 ° C. to 160 ° C. and a time range of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80 ° C. to 140 ° C. and 0.5 to 10 minutes.

The film thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 μm to 30 μm, for example, 0.2 μm to 10 μm, and further, for example, 0.3 μm to 8 μm.

By attaching a mask having a predetermined pattern on the coating film obtained above, irradiating it with light such as ultraviolet rays, and developing it with an alkaline developer, either the exposed part or the unexposed part can be selected depending on the material composition. A sharp relief pattern on the end face can be obtained by heating the washed-out and remaining patterned film at 80 ° C. to 140 ° C. for 0.5 to 10 minutes as needed.

Examples of the alkaline developing solution that can be used include an aqueous solution of an alkali metal hydroxide such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, and hydroxylation such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Examples thereof include an aqueous solution of quaternary ammonium and an alkaline aqueous solution such as an aqueous solution of amines such as ethanolamine, propylamine and ethylenediamine. Further, a surfactant or the like can be added to these developers.

Among the above, a 0.1 to 2.58 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a developer for photoresists, and the photosensitive resin composition of the present invention also uses this alkaline developer. , It is possible to develop well without causing problems such as swelling of the film.

Further, as the developing method, any of a liquid filling method, a dipping method, a rocking dipping method and the like can be used. The developing time at that time is usually 15 to 180 seconds.

After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, followed by air drying with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate and pattern formation. A film is obtained.

Subsequently, the pattern-forming film is post-baked for thermosetting, and specifically, by heating using a hot plate, an oven, or the like, heat resistance, transparency, and flattening property are obtained. , Low water absorption, excellent chemical resistance, etc., and a film having a good relief pattern can be obtained.

Post-baking is generally performed at a heating temperature selected from the temperature range of 140 ° C. to 270 ° C. for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. Is adopted.

Thus, such a postbake makes it possible to obtain a desired cured film having a good pattern shape.

As described above, the photosensitive resin composition of the present invention provides a cured film having high storage stability, sufficiently high sensitivity, very small film loss in the unexposed area during development, and a fine pattern. Can be formed.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The measurement of the number average molecular weight and the weight average molecular weight of the polymer is as follows.
[Measurement of number average molecular weight and weight average molecular weight of polymer]
The measurement of the number average molecular weight and the weight average molecular weight of the polymer was carried out using a GPC system manufactured by JASCO Corporation as an apparatus and Shodex® KF-804L and 803L as columns under the following conditions.
Column oven: 40 ° C
Flow rate: 1 ml / min The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.

The meanings of the abbreviations used in the following examples are as follows.
MMA: Methyl Methacrylate HEMA: 2-Hydroxyethyl Methacrylate HPMA: 4-Hydroxyphenyl Methacrylate HPMA-QD: Condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Compounds synthesized by CHMI: N-cyclohexylmaleimide PFHMA: 2- (perfluorohexyl) ethyl methacrylate TMSSMA: methacrylicoxypropyltris (trimethylsiloxy) silane MAA: methacrylate MAAm: methacrylamide KBM-503: 3-methacryloxypropyl Triethoxysilane P7: A styrene polymer in which a polymer of 85% hydroxystyrene and 15% styrene and a polymer of 70% hydroxystyrene and 30% styrene are mixed at a ratio of 3: 7 AIBN: α, α'-azobisiso Butyronitrile QD: By condensation reaction of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene 1 mol with 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride 2 mol. Compounds to be synthesized GT-401: Butanetetracarboxylate Tetra (3,4-epoxycyclohexylmethyl) Modified ε-caprolactone I907: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE 907, made by BASF)
DEAB: 4,4'-bis (diethylamino) benzophenone DPHA: dipentaerythritol hexaacrylate 8KQ: 8KQ-2001 (alkali-soluble UV curable acrylic resin manufactured by Taisei Fine Chemicals Co., Ltd.)
PGME: Propylene Glycol Monomethyl Ether PGMEA: Propylene Glycol Monomethyl Ether Acetate CHN: Cyclohexanone MIBK: Methyl Isobutyl Ketone TMAH: Tetramethylammonium Hydroxide

<Synthesis example 1>
Acrylic polymer solution (PFHMA 5.00 g, KBM-503 2.87 g, HEMA 1.00 g, CHMI 1.38 g, AIBN 0.51 g was dissolved in PGME 25.14 g and reacted at 80 ° C. for 20 hours. Solid content concentration 30% by mass) was obtained (P1). The obtained acrylic polymer had Mn of 4900 and Mw of 6600.

<Synthesis example 2>
Acrylic polymer solution (solid content concentration 30 mass) was obtained by dissolving 5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN in 25.32 g of PGME and reacting at 80 ° C. for 20 hours. %) Was obtained (P2). The obtained acrylic polymer had Mn of 4800 and Mw of 6700.

<Synthesis example 3>
Acrylic polymer solution (solid content) was obtained by dissolving 5.00 g of PFHMA, 1.16 g of MMA, 1.00 g of HEMA, 1.38 g of CHMI, and 0.43 g of AIBN in 20.93 g of PGME and reacting at 80 ° C. for 20 hours. A concentration of 30% by mass) was obtained (P3). The obtained acrylic polymer had Mn of 4800 and Mw of 6600.

<Synthesis example 4>
Acrylic polymer solution (solid content) by dissolving PFHMA 5.00 g, MAAm 0.98 g, HEMA 1.00 g, CHMI 1.38 g, and AIBN 0.42 g in PGME 20.51 g and reacting at 80 ° C. for 20 hours. A concentration of 30% by mass) was obtained (P4). The obtained acrylic polymer had Mn of 4900 and Mw of 6700.

<Synthesis Example 5>
Acrylic weight was obtained by dissolving 90.00 g of MAA, 225.00 g of HEMA, 45.00 g of HPMA, 180.00 g of MMA, 360.00 g of CHMI and 57.60 g of AIBN in PGME 1436.40 g and reacting at 80 ° C. for 20 hours. A combined solution (solid content concentration 40% by mass) was obtained (P5). The obtained acrylic polymer had Mn of 3100 and Mw of 6100.

<Synthesis example 6>
Acrylic polymer solution (solid content) by dissolving 100.00 g of MAA, 188.89 g of HEMA, 190.37 g of MMA, 262.96 g of CHMI and 47.50 g of AIBN in PGME 1184.59 g and reacting at 80 ° C. for 20 hours. A concentration of 40% by mass) was obtained (P6). The obtained acrylic polymer had Mn of 3800 and Mw of 7300.

<Synthesis example 7>
By dissolving HPMA-QD 2.50 g, TMSSMA 2.58 g, PFHMA 5.26 g, MAA 0.70 g, CHMI 1.46 g, and AIBN 0.33 g in CHN 51.3 g and stirring at 110 ° C. for 20 hours. An acrylic polymer solution (solid content concentration 20% by mass) was obtained (P8). The obtained acrylic polymer had Mn of 7,200 and Mw of 11,000.

<Synthesis Example 8>
5.00 g of PFHMA, 6.70 g of KBM-503, and 0.59 g of AIBN were dissolved in 28.68 g of PGME and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 30% by mass). (P9). The obtained acrylic polymer had Mn of 6700 and Mw of 9800.

<Synthesis example 9>
Acrylic weight is obtained by dissolving 2.29 g of TMSSMA, 4.67 g of PFHMA, 0.47 g of MAA, 1.28 g of HPMA, 1.29 g of CHMI and 0.50 g of AIBN in 24.50 g of PGME and reacting at 80 ° C. for 20 hours. A combined solution (solid content concentration 30% by mass) was obtained (P10). The obtained acrylic polymer had Mn of 3000 and Mw of 4400.

<Examples 1 to 11> and <Comparative Examples 1 to 4>
Examples are obtained by mixing the components (A) to (E) and the solvent with the compositions shown in Table 1 and adjusting the amount of the solvent added so that the solid content concentration of the final composition is 21.0% by mass. The photosensitive resin compositions of 1 to 7 and Comparative Examples 1 and 2 were prepared. Further, the photosensitive resin compositions of Examples 8 to 11 and Comparative Examples 3 to 4 were prepared by adjusting the amount of the solvent added so that the solid content concentration of the final composition was 17.0 by mass. The composition ratio in Table 1 represents the ratio in terms of solid content. In addition, Examples 1 to 10 and Comparative Examples 1 to 3 are positive type photosensitive resin compositions, and Example 11 and Comparative Example 4 are negative type photosensitive resin compositions.

[Evaluation of wettability: Examples 1 to 10 and Comparative Examples 1 to 3]
The photosensitive resin composition was applied onto ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.7 μm. A rectangular pattern having a length of 50 μm and a width of 100 μm is formed on this coating film in a grid pattern so that the bank width is 30 μm. Ultraviolet rays of 5.5 mW / cm ² were irradiated for a certain period of time. After that, it was developed by immersing it in a 2.58% TMAH aqueous solution for 20 seconds, and then washed with ultrapure water for 20 seconds. Next, the coating film on which this rectangular pattern was formed was post-baked and cured by heating at a temperature of 230 ° C. for 30 minutes. A solution of about 20 pl was discharged onto the rectangular opening of the obtained cured film using an Inkjet Designer manufactured by Cluster Technology Co., Ltd. at a drive waveform of B, a repetition frequency of 1 kHz, and a drive voltage of 8 V. As the discharged solution, the solution described in Japanese Patent Application No. 2016-141326, Example 1-1 was used. The results obtained are shown in Table 2.
[Evaluation of wettability: Example 11 and Comparative Example 4]
The photosensitive resin composition was applied onto ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. A rectangular pattern (light-shielding part) with a length of 80 μm and a width of 160 μm is formed on this coating film in a grid pattern so that the bank width is 50 μm, and is 365 nm by Canon's ultraviolet irradiation device PLA-600FA. Was irradiated with ultraviolet rays having a light intensity of 5.5 mW / cm ² for a certain period of time. Then, it was developed by immersing it in a 0.4% TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 30 seconds. Next, the coating film on which this rectangular pattern was formed was post-baked and cured by heating at a temperature of 230 ° C. for 30 minutes. A solution of about 20 pl was discharged onto the rectangular opening of the obtained cured film using an Inkjet Designer manufactured by Cluster Technology Co., Ltd. at a drive waveform of B, a repetition frequency of 1 kHz, and a drive voltage of 8 V. As the discharged solution, the solution described in Japanese Patent Application No. 2016-141326, Example 1-1 was used. The results obtained are shown in Table 2.

<Evaluation criteria for wettability>
◯: The solution is completely wet and spread in the rectangular opening.
X: A portion where the solution is not wet and spread is observed in the rectangular opening.

As shown in Table 2, Examples 1 to 11 had good wettability of the rectangular opening. On the other hand, in Comparative Examples 1 to 4, sufficient wettability could not be confirmed.

Claims (12)

A thermosetting photosensitive resin composition containing the following component (A), component (B), solvent (C) and component (D).
(A) Component: Polymer having the following groups (A1) and (A2) (A1) Liquid-repellent group (A2) Trialkoxysilyl group,
(B) Ingredient: Alkaline-soluble resin,
(C) Solvent,
(D) Ingredient: A quinonediazide compound that is a photosensitive agent. The photosensitive resin composition according to claim 1, wherein the component (A) is a polymer further having the following (A3).
(A3): At least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. The photosensitive resin composition according to claim 1 or 2 , which satisfies at least one of the following (Z1) or (Z2).
(Z1): Further contains a cross-linking agent which is a component (E);
(Z2): The alkali-soluble resin of the component (B) further has a self-crosslinking group, or has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Have more . Claims 1 to 3 in which the liquid-repellent group of the component (A) is at least one group selected from a fluoroalkyl group having 3 to 10 carbon atoms, a polyfluoroether group, a silyl ether group and a polysiloxane group. The photosensitive resin composition according to any one of the above. The photosensitive resin composition according to any one of claims 1 to 4 , wherein the polymer of the component (A) is an acrylic polymer. The photosensitive resin composition according to claim 5 , wherein the acrylic polymer of the component (A) has a number average molecular weight of 2,000 to 100,000 in terms of polystyrene. (B) The photosensitive resin composition according to any one of claims 1 to 6 , wherein the alkali-soluble resin as a component has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene. The photosensitive resin according to any one of claims 1 to 7 , wherein the component (A) is contained in an amount of 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (B). Composition. The invention according to any one of claims 3 to 8 , wherein the component (E) is 1 part by mass to 50 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). Photosensitive resin composition. A cured film made of a thermosetting product of the photosensitive resin composition according to any one of claims 1 to 9 . The display element having the cured film according to claim 10 . A display element having the cured film according to claim 10 as an image forming partition wall.